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Surface modification of a granular


activated carbon by citric acid for
enhancement of copper adsorption

Article in Carbon December 2003


DOI: 10.1016/S0008-6223(03)00197-0

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Carbon 41 (2003) 19791986

Surface modification of a granular activated carbon by citric


acid for enhancement of copper adsorption
J. Paul Chen a , *, Shunnian Wu b , Kai-Hau Chong a
a
Department of Chemical and Environmental Engineering National University of Singapore, 10 Kent Ridge Crescent, Singapore
129791, Singapore
b
Institute of High Performance Computing, 1 Science Park Road, [01 -01, The Capricorn, Singapore 117528, Singapore
Received 19 February 2003; accepted 5 May 2003

Abstract

In this study, citric acid was used to modify a commercially available activated carbon to improve copper ion adsorption
from aqueous solutions. The carbon was modified with 1.0 M citric acid, followed by an optional step of reaction with 1.0 M
sodium hydroxide. It was found that the surface modification reduced the specific surface area by 34% and point of zero
charge (pH pzc ) of the carbon by 0.5 units. Equilibrium results showed that citric acid modification increased the adsorption
capacity to 14.92 mg Cu / g, which was 140% higher than the unmodified carbon. Higher initial solution pH resulted in
higher copper adsorption. The chemical surface modification adversely affected the copper adsorption rate. Adsorption
kinetic mechanisms were investigated with an intraparticle diffusion model. It was found that the modification did not
change both external diffusion and intraparticle diffusion.
2003 Elsevier Ltd. All rights reserved.

Keywords: A. Activated carbon; B. Chemical treatment, Surface treatment; C. Adsorption; D. Adsorption properties

1. Introduction carbon had much higher adsorption of cadmium, lead and


zinc. Lakov et al. [3] modified activated carbons with
Surface modification of activated carbons is recognized 3-methyl-1-phenyl-pyrazolone-5 (HMPP). The copper ad-
as an attractive approach for enhancement of heavy metal sorption capacity was enhanced by 50% even though the
removal. Different heavy metal ions have different af- specific surface area of the carbon decreased by 80%.
finities for different surface functional groups. It has been More recently, Monser and Adhoum [4] reported that,
reported that the affinities between heavy metals and when tetrabutyl ammonium iodide (TBA) or sodium
organic functional groups are different [1]. Modification diethyl dithiocarbamate (SDDC) were applied onto an
can be performed by adsorbing foreign organic compounds activated carbon, a substantial improvement in Cu, Zn and
on the surfaces of carbons. It is well known that activated Cr removal capacity was achieved.
carbons are able to effectively adsorb organic compounds It has been reported that citric acid has a higher binding
in aqueous solutions. This chemical behaviour leads to affinity to copper ions [5]. It is biodegradable and widely
immobilization of organic compounds on the carbon used in the food and pharmaceutical industries. As a result,
surface. it was selected for the modification of a commercially
Surface modification has been studied recently. Ravin- available granular activated carbon in this study. The main
dran et al. [2] impregnated 8-hydroxyquinoline (oxine) on objective of this paper was to compare the adsorption
an activated carbon. It was found that oxine-impregnated performance of citric acid-modified activated carbons with
the unmodified activated carbons. The copper adsorption
*Corresponding author. Tel.: 165-6874-8092; fax: 165- equilibrium and kinetics were determined. Langmuir and
6779-1936. Freundlich isotherm equations were employed to quantify
E-mail address: checjp@nus.edu.sg (J.P. Chen). the adsorption equilibrium. The effect of solution pH on

0008-6223 / 03 / $ see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016 / S0008-6223(03)00197-0
1980 J.P. Chen et al. / Carbon 41 (2003) 19791986

copper ion adsorption behaviour was examined. An in- pure nitrogen gas overnight at a temperature of 150 o C to
traparticle diffusion model was used to investigate the remove any contaminants as well as moisture that might be
adsorption mechanisms. present on the activated carbon surfaces.
The surface morphology of the activated carbon samples
was visualized by scanning electron microscopy (JEOL,
2. Experimental JSM-5600V, Japan). SEM enables the direct observation of
any surface microstructure changes in the activated car-
2.1. Materials bons that would have occurred due to the citric acid
modification.
In this study, Fitrasorb 200 (Calgon, Pittsburgh, PA, Potentiometric titration experiments were carried out
USA) was used. Copper chloride dihydrate from J.T. Baker with an automatic titrator (Metrohm 716 DMS Titrino,
(Phillipsburg, USA), and sodium nitrate, lead nitrate, Switzerland). A 0.25-g amount of activated carbon was
sodium hydroxide, sodium acetate, acetic acid, hydrochlo- added to a conical flask containing 50 ml of 0.1 M sodium
ric acid, nitric acid and citric acid monohydrate from nitrate as background ionic strength. The solution was
Merck (Germany) were used. All chemicals were of shaken for 48 h on a shaker. The titration was carried out
reagent grade. Solution pH was adjusted by 0.1 M HCl or using 0.1 M NaOH and 0.1 M HNO 3 solutions.
0.1 M NaOH. The citric acid has a chemical formula of
HOOCCH 2 COH(COOH)CH 2 COOH, indicating that 2.4. Adsorption equilibrium
it is a small organic compound rich in carboxylic groups.
The concentration of metal ions was measured using The activated carbons of varying amounts were added to
inductively coupled plasma emission spectroscopy (ICP- conical flasks that contained 100 ml buffered or unbuffered
ES) (Perkin-Elmer Optima 3000, USA). Samples were CuCl 2 solutions. Buffered solution with a pH of 4.9 was
acidified with concentrated nitric acid, and filtered with a comprised of 0.07 M sodium acetate and 0.03 M acetic
0.45-mm Whatman Autovial filter (USA) before analysis. acid. The unbuffered solutions pH values ranging from 3
Solution pH was measured using an Accumet basic pH to 11 were adjusted by adding HCl or NaOH. The
meter (Fisher Scientific, USA). solutions were shaken on a shaker with temperature
controlled at 25 8C for 48 h in order to reach equilibrium.
2.2. Preparation of citric acid-modified and base- The final samples were analyzed using ICP-ES.
extracted activated carbons
2.5. Adsorption kinetics
The activated carbon was ground and sieved to retain
the 2032 mesh fraction. It was washed with deionised A 10-g amount of activated carbon was added to 1000-
(DI) water to remove fine powdered activated carbon left ml buffered or unbuffered 1310 24 M CuCl 2 solution. The
after sieving. It was then left to dry in an oven at 110 8C solution was then stirred at a constant rate. Samples were
for 2 h and denoted by WAC. taken at different time intervals and analysed using ICP-
The WAC was reacted with a 1 M citric acid solution at ES. The pH was 4.9 in the buffered solutions; while the
a ratio of 4 g activated carbon to 25 ml citric acid solution. initial and final pH values were 5.0 and 5.2 in the
It was shaken for 30 min before being dried at 50 8C unbuffered solutions.
overnight. The citric acid modified activated carbon was
then washed with DI water until no turbidity could be
observed when a 0.1 M lead nitrate solution was added to 3. Results and discussion
the washed liquid. The modified activated carbon was
dried at 110 8C for 2 h and referred to as CAC. 3.1. Specific surface areas of activated carbon samples
A fraction of CAC was continuously washed with a 1 M
sodium hydroxide solution for at least 2 h. It was then As represented in Table 1, the surface area is 648 m 2 / g
washed with DI water to remove the excess sodium for the WAC, similar to the value reported by Corapcioglu
hydroxide until no pH variation in the washed liquid could and Huang [6], but lower than 1008.8 m 2 / g reported by
be detected. This base-extracted CAC was then dried at Chen and Lin [7]. The difference could be due to the
110 8C for 2 h and referred to as SAC. removal of considerable organic by-products and minerals
present in the activated carbon surface. In this study, the
2.3. Surface properties carbon was washed between 20 and 30 times until the pH
and the conductivity of the water samples became con-
The specific surface areas of the activated carbon stant; while the carbons were normally washed 35 times
samples were determined using a NOVA 300 BET analyzer in most of studies (e.g., Chen and Lin [7]).
(QuantaChrome, USA). Before adsorption isotherms were The citric acid modification of the activated carbon
obtained, the activated carbon sample was purged with further reduces the surface areas of CAC and SAC by 34
J.P. Chen et al. / Carbon 41 (2003) 19791986 1981

Table 1
Summary of specific surface areas of activated carbon samples
Carbon type Description Specific surface area (m 2 / g)
WAC Unmodified activated carbon 648
CAC Citric acid modified activated carbon 431
SAC Sodium hydroxide-extracted CAC 448

and 31%, respectively. This could arise from pore block- reduction in the surface area of CAC as compared with
age by adsorbed citric acid molecules. Because of its small that of WAC (Table 1). It implies that the adsorption
molecular size, citric acid can easily access the pore kinetics in CAC may be much slower than that in WAC
structure of the activated carbon. This finding is consistent since clogging of the cracks and cavities can lead to
with the results reported by Ferro-Garcia et al. [8], resistance in the metal transport from the solution to the
indicating that the surface area of activated carbon de- adsorption sites.
creased from 1086 to 643 m 2 / g after adsorption of gallic
acid [(HO) 3 C 6 H 2 CO 2 H]. Some surface area of CAC is 3.3. Potentiometric titration
recovered after sodium hydroxide treatment. This may be
partially attributed to the removal of the organic substances The effect of the modification was investigated by
within the pore structure, which are soluble in alkali potentiometric titration of the carbon samples before and
solution. after modification. The amphoteric behaviour of activated
carbons can be described by the following ionisation
3.2. SEM micrographs reactions [6,7]:

SOH 1 H SOH 2
1 1
Fig. 1 shows the SEM micrographs of activated carbon Ka1 (1a)
samples before and after citric acid modification. It dem-
onstrates that there are considerable small cavities, cracks SOH SO 1 H
2 1
Ka2 (1b)
and attached fine particles over the activated carbon
surface, forming a system of complicated pore networks. where SOH represents a generalized surface functional
Comparison of these micrographs shows that the modi- group.
fication does not significantly change the morphology of The potentiometric titration data were used in the
the surface matrix of the carbons. However, the citric acid determination of the above the intrinsic surface acidity
modification reduces the number of cracks and cavities on constants (Ka1 and Ka2 ) and the concentration of surface
the carbon surface, which are clogged by the adsorbed functional group of carbons (SOH). An equilibrium con-
citric acid molecules. This also explains the reasons for the stant searching program, called FITEQL developed by

Fig. 1. SEM micrographs of the surfaces of the carbons: (a) WAC; (b) CAC.
1982 J.P. Chen et al. / Carbon 41 (2003) 19791986

3.4. Copper ion adsorptive isotherms at controlled pH

Copper ion adsorption capacities of various activated


carbons at pH 4.9 were calculated by best-fitting the
experimental results with least-square regression to the
Langmuir isotherm model, which is expressed by the
following equation:

qmax bCe
qe 5 ]] (2)
1 1 bCe

where qe is the amount of Cu 21 adsorbed at equilibrium


(mg / g), Ce is the equilibrium concentration of copper in
solution (mg / l), qmax is the maximum adsorption capacity,
b is the Langmuir constant related to heat of adsorption.
The Langmuir plots for copper isothermal adsorption
data at controlled pH are shown in Fig. 3a. It demonstrates
that the Langmuir adsorptive isothermal equation fits the
experimental data well. Comparison of the qmax values in
Table 3 shows that the CAC has 143% higher copper
Fig. 2. Experimental and modelled titration curves for WAC and adsorption capacity than WAC, which is very consistent
CAC. with the enhancement in the surface site density. This
indicates that the apparent reduction in the surface areas of
Herbelin and Westall [9] was employed. The experimental the carbons does not adversely affect copper adsorption.
data and modelling fitting curves for the titration of WAC The immobilization of citric acid on the activated carbon
and CAC are given in Fig. 2. The modelling results for surface introduces more surface adsorptive sites (mainly
both WAC and CAC are in good agreement with the carboxylic functional groups from the citric acid), which
experimental data. The adsorption constants and the con- provide additional copper ion binding capacity. The im-
centration of surface functional group are given in Table 2. mobilization of citric acid may also change the nature of
The surface site density, calculated from the concentration the carbon surface from hydrophobic to hydrophilic, which
of surface functional group and specific surface area, is facilitates the access of copper ions to surface adsorption
0.18 sites / nm 2 for WAC and 0.44 sites / nm 2 for CAC. sites. The copper adsorptive capacity of SAC is 93%
These values are in good consistence with the reported higher than that of the WAC; however, it is lower than that
values of 0.05|0.3 sites / nm 2 for granular activated car- of the CAC. This might result from removal of organic
bons by Corapcioglu and Huang [6]. Citric acid modi- substances by the alkali NaOH solution. These substances
fication increases the surface site density by 144%, indicat- can also participate in the metal binding process and
ing that the modified activated carbon would greatly contribute to copper adsorption.
enhance its metal adsorption capacity. It is noteworthy that the correlation coefficients (r 2 ) in
The intersection points of the titration curves with the linear regression are 0.9940 and 0.9996 for CAC and
solution pH axis are defined as point of zero charge SAC, respectively, which are higher than 0.9826 for WAC.
(pH pzc ). The pH pzc values for WAC and CAC are 7.07 and It suggests that the activated carbon surface becomes more
6.54, respectively. The pH pzc result of WAC is in good homogenous after the modification. The citric acid con-
agreement with that of Chen and Lin [7]. The pKa and tains carboxylic functional groups. They can fully cover
pH pzc values of CAC show that it is more acidic than the the carbon surfaces when the modification is applied,
WAC due to the modification. which results in homogeneous surfaces of the carbons.

Table 2
Surface site properties of activated carbon samples*
Carbon type WAC CAC
Concentration of surface functional groups (mmol / g) 0.19 0.32
Surface acidity constants
pKa1 4.52 3.98
pKa2 8.42 8.77
pH pzc 7.07 6.54
* Units: Ka1 : M 21 ; Ka2 : M.
J.P. Chen et al. / Carbon 41 (2003) 19791986 1983

Higher content of carboxylic functional groups can sig-


nificantly improve the adsorption as the affinity between
metals and the group is very high [1].
To explain the observed adsorption equilibrium more
clearly, the Freundlich isotherm model is also used:

qe 5 Kf C e1 / n (3)

where Kf is Freundlich adsorption constant, 1 /n is a


measure of adsorption intensity.
Freundlich plots for the copper adsorption at pH 4.9 are
shown in Fig. 3b. It illustrates that adsorption of copper
ions onto these activated carbons obeys Freundlich iso-
therm model as well. The calculated constants Kf and 1 /n
are given in Table 3.
1 /n,1 in Table 3 indicates an unfavourable adsorption
reaction. In other words, the increase in the equilibrium
concentration in the solid phase (qe ) is lower than that in
the solution phase (Ce ). This suggests that with progressive
coverage of activated carbon surface, the repulsive forces
among the copper ions (e.g., electronic and Coulombic
repulsion) become more dominant than the attractive forces
(e.g., Van der Waals forces) [10]. Hence, copper ions
manifest a weaker tendency to adsorb onto the activated
carbon surface.
The Freundlich equation is based on an assumption of
adsorption onto heterogeneous surfaces. The correlation
coefficient in the linear regression is 0.9934 for WAC,
much higher than the values for CAC and SAC. Hence, it
confirms that the surface of WAC is more heterogeneous
than that of citric acid modified activated carbons. This
heterogeneity arises from the large number of different
functional groups on activated carbon surface (e.g., car-
boxylic, carbonyl, hydroxyl, ether, phenolic, quinine, and
lactonic groups) and the various adsorbentadsorbate
interactions.

3.5. pH effect on copper adsorption

Adsorption of copper ions onto the carbons at different


initial pH is shown in Fig. 4. It demonstrates that the
copper adsorption by the WAC is strongly pH dependent.
Fig. 3. Copper isothermal adsorption at pH 4.9: (a) Langmuir plot, The copper adsorption sharply increases when the solution
(b) Freundlich plot. pH is increased from 3 to 4, which is in consistence with
the observations reported in the literature [6,7]. The copper

Table 3
Adsorption isotherm constants at pH 4.9*
Carbon type Langmuir constants Freundlich constants
qmax b r2 Kf 1 /n r2
WAC 6.14 0.18 0.9826 2.16 0.24 0.9934
CAC 14.92 0.08 0.9940 1.66 0.57 0.9025
SAC 11.85 0.20 0.9996 2.72 0.38 0.9361
* Units: qmax : mg / g; b: (mg / l)21 ; Kf : (mg / g) /(mg / l)1 / n .
1984 J.P. Chen et al. / Carbon 41 (2003) 19791986

Fig. 4. Effect of initial solution pH on copper adsorption.

ion adsorption is mainly due to the strong dependence of


dissociation of surface functional groups on the solution
pH. As pH increases, more surface functional groups
dissociate to provide metal binding sites, which results in
higher metal ion adsorption. The interaction of copper ions
with activated carbon can be described as:

SOH 1 Cu 21 SOCu 1 1 H 1 (4a)

SOH 1 Cu 21 1 H 2 O SOCuOH 1 2H 1 (4b)

The dissociation constant of citric acid is 3.1 [11], which


suggests that citric acid modified activated carbon should
show high copper adsorption at solution pH of above 3.1.
This is confirmed in Fig. 4. CAC adsorbed nearly 85%
copper ions from the aqueous solution even at solution pH
of about 3.5, while SAC adsorbed nearly 100% copper
ions at the same solution pH. It suggests that citric acid Fig. 5. Kinetics of copper adsorption: (a) observation, (b) in-
traparticle diffusion.
modified activated carbon can be applied efficiently in a
wider pH range.
fication, citric acid is adsorbed to the surfaces of carbons,
3.6. Adsorption kinetics which reduces the effective diameter of the mi-
croporosities. This in some cases may actually prevent
Fig. 5 shows copper ion adsorption kinetics on the further adsorption of other substances. The measurement
carbons. It illustrates that adsorption follows a first rapid of the specific surface area by the BET analyzer is based
step and a second slow step. Adsorption kinetics of the on adsorption of nitrogen gas. Our BET measurement
surface modified activated carbons is much slower than shows that the modification reduces the specific surface
that of WAC. The adsorption equilibrium times are 6, 10, area by 34% (see CAC versus WAC in Table 1). There is
and 20 h when WAC, CAC and SAC are used, respective- not much difference between WAC and CAC in adsorption
ly. Immobilization of citric acid on the activated carbon kinetics as shown in Fig. 5a. Comparison of nitrogen
surfaces impedes the access of copper ion to the adsorption adsorption in the BET measurement and metal adsorption
sites, which are consistent with the findings in the specific kinetics indicates that the copper uptake is not so critically
surface area and the SEM micrographs. In the modi- dependent on adsorption potentials within porosities.
J.P. Chen et al. / Carbon 41 (2003) 19791986 1985

It can be assumed that the adsorption of copper ions mum adsorption capacity increased from 6.14 mg Cu / g
onto the activated carbons follows mainly these three WAC to 14.92 mg Cu / g CAC and 11.85 mg Cu / g SAC,
consecutive steps of external diffusion, intraparticle diffu- respectively. After the modification, the activated carbon
sion, and finally adsorption reactions. One or more of these surface became more homogeneous; while its specific
steps can control the adsorption kinetics. In most cases, the surface area decreased significantly.
adsorption reactions occur rapidly. Therefore, the first two The adsorption kinetics of the modified carbons was
steps are normally important in the kinetics. There are a slower than that of the unmodified carbon. The modi-
series of theoretical models available to describe the fication does not change both external diffusion and
adsorption kinetics [7,12]. However, the mathematical intraparticle diffusion properties.
solutions are pretty complex and require more input Effect of initial solution pH on the copper adsorption
information, such as adsorption reaction constants. onto the citric acid modified carbons was insignificant;
A simplified intraparticular diffusion model was also however, it became important when the unmodified carbon
employed to elucidate the adsorption mechanisms. It was was used. These modified carbons were able to maintain
first developed by Weber and Morris [13] and has been high metal adsorption capacity in very wide pH range.
used in adsorption kinetic studies [14]. It is assumed that Therefore, they can be useful in treating wastewater with a
the adsorption is controlled by three stages: the first wider pH range.
sharper linear stage being a rapid external diffusion and
surface adsorption; the second linear stage being a gradual
adsorption stage, where the intraparticle diffusion is rate-
Acknowledgements
limited; and the final stage being final equilibrium stage
where the intraparticle diffusion starts to decrease due to
The financial support provided to J.P.C. by the National
low concentration in solution phase as well as less
University of Singapore under RP-3981604 and R-279-
available adsorption sites.
000-104-112 is appreciated.
Adsorption capacity (q, mg / g) can be plotted against
t 1 / 2 . As shown in Fig. 5b, the adsorption has three stages.
The first stage in the four adsorption cases is completed in
about 6.25 min. The second stages in the cases demon- References
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